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Robert M BurgessOffice of Research and Development, NHEERL, Atlantic Ecology Division
Narragansett, Rhode Island [email protected]
&
Marc S GreenbergOffice of Solid Waste and Emergency ResponseOSRTI/TIFSD/Environmental Response Team
Edison, New Jersey [email protected]
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites:
Concepts, Samplers, Methods & Applications
SAMS #3
• Portions of presentation will follow the outline of this document
– Released December 2012– Provides introduction to
passive sampling– Intended for use by
remedial project managers (RPMs)
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Outline
• Why use passive samplers and what they tell us• Types of passive samplers and how they work• Selecting, preparing, deploying, recovering, and storing passive
samplers• Analyzing passive sampler data and a brief case study• Scientific challenges in using passive samplers• US EPA contacts working with passive samplers• Application at Superfund Sites• Summary
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Conceptual Model (i.e., Cartoon) of Relationship BetweenContaminated Sediments and Aquatic Life
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Atmosphere
Water
Contaminated Sediments
Dissolved and BioavailableConcentration
Diffusion/Advection
Inte
rstit
ial
Wate
rSed
imen
t
Partic
le
PCB
Molecule
Dissolved and BioavailableConcentration
Is there another sampling method for collecting and measuring dissolved and bioavailable
contaminants?
• How to determine or measure dissolved and bioavailable concentrations in the water column and interstitial waters?
– Why not continue to use conventional sampling methods? Some problems:
– Water Column
• Logistically and technically difficult to collect large volumes of surface water and extract
• Several artifacts including losses to filters and surfaces and contamination by colloids and small particles reduce accuracy of analysis
• Analytical detection limits are often not sufficiently low
– Interstitial Water
• Centrifuge or squeeze interstitial water results in limited volumes• Similar artifacts as water column• Collecting large volumes of interstitial waters is logistically challenging,
scientifically dodgy and generally expensive
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Introduction
√
√
Introduction• Passive sampling
– Developed in the 1980s
• Analytical chemistry, food sciences, pharmaceuticals
– Used in environmental sciences since the early 1990s
• Water column, soils, groundwater, sediments
– Consist of an organic phase (i.e., simple organic film or polymer) which accumulates contaminants from the dissolved phase
• Polyethylene (PE) • Polyoxymethylene (POM)• Solid phase micro-extraction (SPME)• Semi-permeable membrane devices (SPMDs)
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Introduction
• Types of contaminants sampled
– Hydrophobic or Nonionic Organic Contaminants
• Low water solubility
• Highly lipiphillic and bioaccumulating (medium to large KOWs)
• Contaminants of Concern (e.g., PCBs, PAHs, Chlorinated pesticides, Dioxins/Furans)
– Not Metals
• Methods are under-development
• Not as advanced or established as methods for hydrophobic organic contaminants
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Why Use Passive Samplers? The Advantages
• Analytically– Passive samplers accumulate contaminants over time during
their deployment– Detection limits are less of a problem
• Representativeness of data– Passive samplers are deployed in the environment for prolonged
periods of time– “Time-averaged” or “time-integrated” measurement– Reflects representative concentrations at a site rather than
“snap-shot” of conditions
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
√
√
• Expense– Preparation and chemical analysis of passive samplers is
about $100 - $200 less than the conventional method
• As commercial laboratories establish experience with extracting and analyzing passive samplers – the prices are likely to drop
• Extraction/analyses of passive samplers is less challenging than sediment/soil or tissue samples
– Passive samplers are inexpensive
• If lost during deployment (e.g., storm, vandalism) not a great cost
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Why Use Passive Samplers? The Advantages
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
a Costs provided courtesy of an independent laboratory. Cost values in dollars are reported per sample.b Assume 10 - 20 samples, GC/MS analysis of NOAA PCB list (20 congeners)
Table 2. Comparison of costs for analyzing different types of samples for 20 National Oceanic and Atmospheric Administration (NOAA) PCBs. • Expense
Type of Water Column Sample
Materials(samplers & deployment
equipment) ($)
Preparation of Extract & Chemical
Analysis ($)Total ($)
Water (5 L by conventional method)
<5 525 530
Polyethylene (PE) ~5 375 380
Polyoxymethylene (POM) ~50 375 425
Solid Phase Micro-extraction (SPME)
~35 275 310
What Passive Samplers Tell Us
(1) Concentration of COCs in passive sampler• Evidence of correlation with bioaccumulation by aquatic organisms
• Serve as surrogates for biomonitoring organisms– Especially in situations where mussels or fish cannot be used
(e.g., low dissolved oxygen, toxicity, low/high temperature constraints)
(2) Dissolved concentrations of COCs in water around passive sampler
• Water column• Interstitial water• Compare to Water Quality Criteria (WQC) or other water quality
standards or toxicity data
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The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
√
√
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Time (days)
Dis
solv
ed C
once
ntra
tion
(ng/
L)
0 30
Storm event withsediment resuspension
Flooding
Ship traffic withsediment resuspension
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Passive sampler-basedconcentration
Actualconcentration
What Passive Samplers Tell Us
“Time-averaged” or“time-integrated”
measurement
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Atmosphere
Water
Contaminated Sediments
Dissolved and BioavailableConcentration
Conceptual Model (i.e., Cartoon) of Relationship BetweenContaminated Sediments and Aquatic Life
Atmosphere
Water
Contaminated Sediments
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Types of Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Polyethylene (PE) Polyoxymethylene (POM)
PE25 - 50 µm thick
POM
75 µm thick
0.2
5 m
2.5 cm
Types of Passive Samplers
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SPME
2.5 cm 210 um inner
glass core
10 - 100 um outer
polydimethylsiloxane (PDMS)
coating
fiber-optic cable
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
2.5 cm
50 - 95 um thick polyethylene shellcontaining synthetic lipid triolien
cross-section SPMD
triolien layer
Solid PhaseMicroextraction (SPME)
Semi-PermeableMembrane Device (SPMD)
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Types of Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
HI
CIH
HI
CIH
HI
CIH
HI
CIH
HI
CIH
HI
CIH
(a)
(c)
(b)
HI
H - C - HI
SiI
H - C - HI
H
O
HI
H - C - HI
SiI
H - C - HI
H
O
HI
H - C - HI
SiI
H - C - HI
H
O
HI
H - C - HI
SiI
H - C - HI
H
HI
CIH
HI
CIH
HI
CIH
HI
CIH
OO O
Polyethylene
Polydimethylsiloxane
Polyoxymethylene
Atom Key:
White = Hydrogen
Black = Carbon
Red = Oxygen
Grey = Silicon
Dioxin molecule(green = chlorine)
“Like Dissolves Like”(i.e., contaminants dissolve into the polymers)
Some Theory on How Passive Samplers Work
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Water Column
50 u
m
Passive Sampler(e.g., PE or POM)Initial concentration of PCBs in
passive sampler = 0 ng/g
PCB molecule
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Some Theory on How Passive Samplers Work
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Deployment Time (days)
Con
cent
ratio
n(n
g/g
Pas
sive
Sam
pler
)
Equilibrium Sampling
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
CC
KDSampler
Sam pler D
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Deployment Time (days)
Con
cent
ratio
n(n
g/g
Pas
sive
Sam
pler
)
* = Equilibrium
*
Dissolved andBioavailable
Concentration
where, CD is the dissolved concentrationof a contaminant (ng/mL),CSampler is the passive samplerconcentration (ng/g),KSampler-D is the passive sampler-dissolved partition coefficient (mL/g)
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Some Theory on How Passive Samplers Work
√
√
√
Equilibrium Sampling
• General guidance presented today (SAMS #3 document)
• Society of Environmental Toxicology and Chemistry (SETAC)– Pellston Technical Workshop on passive sampling (Fall 2012)– Series of scientific papers to be published in 2014 including practical
guidance for field deployments (e.g., QA/QC)
• Strategic Environmental Research and Development Program (SERDP) and Environmental Security Technology Certification Program (ESTCP)– Funding project developing specific guidance using passive samplers at
contaminated sites (due late 2014/early 2015)– Published as a U.S. EPA document– Contents: SOPs for field deployment/recovery, chemical analysis,
QA/QC considerations– Designed for use by contractors and contract laboratories
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Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
√
Preparing, Deploying, Recovering, and Storing Passive Samplers
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
• Samplers must be free of contaminants prior to deployment
– Samplers soaked in organic solvent to remove organic contaminants & soaked in deionized water to remove organic solvent from polymer structure
– Samplers wrapped in aluminum foil, placed into a plastic bag, and stored at - 4ºC until deployment
– Samplers transported to the field in clean ice-filled cooler(s)
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Water Column Deployment
Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
(NHEERL & MIT)
PE
Stainless steel ring
SPME (in coppermesh envelope)
PE
POM
(NHEERL & Brown U)
Minnow trap
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Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Water Column Deployment
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Sediment Deployment
(SCCWRP)
Copper tubinghousing
SPME (in protective syringe)
SPME (in protective syringe)
Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
(U Texas)
SPME (insidestainless steel tube)
(Aarhus U, Denmark)
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Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
PE or POM (in aluminum frame)
Sediment Deployment
(MIT)
PE or POM (in aluminum frame)
(MIT)
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Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Sediment Deployment
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Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
OSRTI’s Environmental Response Team Dive Team & Region 10’s Dive Team have extensive experience deploying and recovering passive samplers – cost-effective resource
(MIT
& R
egio
n 9)
Diver-assistedsediment deployment
SedimentDeployment
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Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
PE and POM(in aluminum frames)
(NHEERL )
(NH
EE
RL
)
SPME in copper tubing SedimentDeployment
Platform when deployedSamplers below
sediment surface
Samplers above
sediment surface
Measure of
contaminant flux into
the water column
• After the deployment period (~ 28 days)
– Samplers removed from deployment gear (e.g., stainless steel rings, copper tubing, minnow cages, frames)
– Samplers wiped clean with laboratory tissue and/or quickly rinsed with clean water
– Samplers wrapped in aluminum foil or placed in clean glass jars (with teflon-lined lids) and returned to the laboratory in a clean cooler(s) on ice (as soon as possible)
– Samplers stored at - 4ºC in the dark until organic solvent extraction and chemical analyses are performed
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Preparing, Deploying, Recovering, and Storing Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Selecting Passive Samplers
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Passive Sampler Advantages Disadvantages
Polyethylene (PE) ● Inexpensive polymer● Robust and rugged● Easy to work with ● Simple to deploy and recover● Not limited by sample mass (greater analytical sensitivity)● Will stretch during deployment before it rips● Increasing use globally● Good for both water column and sediment deployments
● Slower equilibration than SPME● Folds on itself, making cleaning difficult
Polyoxymethylene (POM) ● Inexpensive polymer● Robust and rugged● Easy to work with ● Simple to deploy and recover● Not limited by sample mass (greater analytical sensitivity)● Cleans easily● Increasing use globally● Good for both water column and
sediment deployments
● Slower equilibration than SPME● Can rip easily compared with PE
Solid Phase Microextraction (SPME) ● Inexpensive polymer fibers● Rapid equilibrium● Widely used globally● Once protected, simple to deploy and recover● Clean easily● Good for sediment deployments
● Fragile – need to protect during deployment● Relatively difficult to handle● Limited polymer mass (less analytical sensitivity)● Poor for water column deployments because of the limited polymer mass
• Raw data (from the analytical laboratory)– Measured concentration of contaminants in the
passive sampler (CSampler)• Units
– µg/g sampler– µg/mL sampler (convert to µg/g sampler by dividing by
the passive sampler density (e.g., PE = 0.92 g/mL))
• Calculate contaminant dissolved concentration (CD) (g/mL):
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Analyzing Passive Sampler Data
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
CC
KDSampler
Sam pler D
Sampler-Dissolved Partition Coefficient (mL/g):Several are available in the SAMS #3 document,
the SETAC papers, the SERDP/ESTCP guidance, the scientific literature
• Palos Verdes Shelf Superfund Site– Water Column and Sediment Deployments
• Located off of the coast of Los Angeles (CA)• Carmen White and Judy Huang (RPMs)• Deep water marine site (60 m)• Contaminants of Concern: DDTs & PCBs• 12 water column stations
– 5 m from surface; 30 m; 5 m above bottom• Five sediment stations
– Objectives
• Determine water column concentrations of contaminants resulting from remediation activity (before, during, after)
• Determine magnitude of flux of contaminants into the water column from sediment stations
• Compare different types of passive samplers (PE, POM, SPME)
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Brief Case Study
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
√√
√
Brief Case Study
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Water Column Deployment Stations (2010)
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2500
1250
1875
625
0Dis
solv
ed C
onc
entr
atio
n (p
g/L)
Exceed Human HealthAWQC
Exceed Human
Health and Aquatic Life
AWQC
PE-based p,p’ DDE Dissolved Concentrations (5 m above bottom)
Brief Case Study
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
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Brief Case Study
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
300
150
225
75
0Dis
solv
ed C
onc
entr
atio
n (p
g/L)
Exceed Human HealthAWQC
PE-based Total PCB Dissolved Concentrations (5 m above bottom)
35 of 43
Brief Case Study
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Sediment Deployment Stations (2011)
0 5 10 15 20 25
25
15
5
-5
-15
-25
De
pth
(cm
)
Dissolved Concentration(ng/L)
p,p’-DDE Station 6C
Sediment
Water Column
Flux = 260 ngp,p’-DDE/cm2 y
• Establishing when equilibrium between the contaminants and passive sampler occurs
– Unless deployment time series data is available (i.e., $$$)– Challenge in all monitoring (including biomonitoring)– Solution: Use of performance reference compounds (PRCs) loaded
into the passive sampler to predict equilibrium• PED, POM• SPME assume very rapid equilibration
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Deployment Time (days)
Co
nce
ntr
atio
n(n
g/g
Pa
ssiv
e S
am
ple
r) *
Scientific Challenges in using Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
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Water Column
50 u
m
Polyethylene
Polybrominatedbiphenyl ether
(PBDE)
Initial concentration of PBDEs inpassive samplers is known
Scientific Challenges in using Passive Samplers
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Deployment Time (days)
Con
cent
ratio
n(n
g/g
Pas
sive
Sam
pler
)Scientific Challenges in using Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
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Deployment Time (days)
Con
cent
ratio
n(n
g/g
Pas
sive
Sam
pler
)
PCB
PRC
Scientific Challenges in using Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
CSampler –Equilibrium Adjusted
Animal Concentration (ng/g) = ά + β*Sampler Concentration (ng/g)
• Relating passive sampler uptake of contaminants to animal bioaccumulation
– Critical for determining how to interpret passive sampler data
– Dataset comparing passive sampler uptake to animal bioaccumulation is being established
– Solution: Generate general linear models:
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Passive Sampler (e.g., PE or POM) Mussels
?=
Scientific Challenges in using Passive Samplers
26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
100
1000
10000
100000
1000000
100 1000 10000 100000 1000000
Wor
m C
once
ntra
tion
(ng/
g)
PED Concentration (ng/g)
1:1 Line
r2 = 0.88
Friedman et al. (2009)
Polychaete
US EPA Contacts Working with Passive Samplers
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26 August2013
The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
Name Office and Location e-mail
Robert Burgess ORD/NHEERL/AED-Narragansett, RI [email protected]
Lawrence Burkhard ORD/NHEERL/MED-Duluth, MN [email protected]
Mark Cantwell ORD/NHEERL/AED-Narragansett, RI [email protected]
Bruce Duncan Region 10 – Seattle, WA [email protected]
Marc Greenberg OSWER/OSRTI/ERT-Edison, NJ [email protected]
Judy Huang Region 9 - San Francisco, CA [email protected]
Matthew Lambert OSWER/OSRTI/Washington, DC [email protected]
Marc Mills ORD/NRMRL/ LRPCD-Cincinnati, OH [email protected]
Joseph Schubauer-Berigan ORD/NRMRL/ LRPCD-Cincinnati, OH [email protected]
Sean Sheldrake Region 10 - Seattle, WA [email protected]
Rachelle Thompson Region 9 - San Francisco, CA [email protected]
Summary
• Passive sampling is a scientifically sound and cost-effective approach for monitoring contaminant concentrations– water column– sediment interstitial waters
• Passive samplers provide information on:– Dissolved and bioavailable contaminant concentrations– Sampler uptake may serve as a surrogate for animal bioaccumulation
• Applications include:– Monitoring water column and interstitial water concentrations before,
during and after remediation– Determining sources of contaminants released from sediments to the
water column (e.g., site model development)– For many applications, passive sampling is the future of environmental
sampling
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The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites
√
√
√
Acknowledgements
• OSWER, specifically OSRTI (e.g., S. Ells, M. Lambert)• L. Fernandez (U.S. EPA/Northeastern Univ.) & M. Perron
(U.S. EPA)• Y. Burhan (Tetra Tech)• Reviewers of the SAMS document• Sources of photographs in the SAMS document• See SAMS document for more specifics
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The Use of Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites